Catalytic polymerization of acetylene



Patented J1me is, 1939 l V 2,152,373 UNITED STATES PATENT QFFICE CATALYTIC POLYMERIZATION F ACETYLENE Albert S. Carter, Wilmington, and Howard W.

Starkweather, New Castle County, Del.-, assignors'to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application July 2, 1937, Serial No.'151,644

6 Claims. (01. 260-67 8) This invention relates to the manufacture of These objects have been accomplished by prononbenzenoid acetylene polymers. More particviding a novel catalyst composition comprising ularly it relates to a process for the manufacture ammonium chloride and cuprous chloride of vinylacetylene from acetylene, and still more (CuzClz) in approximately the molecular proparticularly, to:a catalyst especially adapted to portions of 2 to 1 in water, and polymerizing 5 r the manufacture of monovinylacetylene. acetylene in the presence of this catalyst. It

In United States Patent 1,811,959, issued June has been-found that, as in the case of prior 30, 193.1, to Julius A. Nieuwland is described a catalyst compositions, the polymer production process for the polymerization of acetylene in increases with increase in temperature. Unlike the presence of aqueous solutions of cuprous the prionart, the yield of monovinylacetylene by 10 salts. In a subsequent patent to Carter and polymerization of acetylene, in the presence of Downing, (United States Patent No. 2,048,838, thisnovel catalyst is unexpectedly practically issued July 28, 1936), special conditions and unaffected by temperature variation within the technique of operation were described to provide range of good polymer production. Since dia method of producing monovinylacetylene in vinylacetylene is the principal by-product, it is 15 high yields. In this prior art, it was shown that convenient to express all of the higher polymers an aqueous solution of cuprous chloride and am: as divinylacetylene, although the products other monium chloride would polymerize acetylene to than divinylacetylene may amount to as high as ,a mixture of monovinylacetylene and vdivinyl- 15% of thetotal by-products. With all of the acetylene; it was further stated that .ternperaby-products expressed as divinylacetylene, the 20 tures up to 100 0. could be satisfactorily used. ratio of monovinylacetylene to by-products may In the prior art processes, composition of catabe called the MVA/DVA ratio. This term will lyst and other conditions remaining the same, be so used hereinafter. Using this terminology, increase in temperature to an optimum value theabove advantages of the new catalyst combelow 100 C. has resulted in an increase in the position may be restated by saying that the 25 production of acetylene l ym sw ve in- MVA/DVA ratio of the products'of polymerizacrease in temperature also resulted in an increase tion of acetylene in the presence of the new in the proportion of higher polymers to monocatalyst in the temperature range of good polyvinylacetylene; i. e., with fixed catalyst composi mer production is substantially unaffected by tion and reaction conditions per unit amount of temperature. This means that the process can 30 acetylene polymerized, increase in te perature be carried out at the temperature which favorsresulted in a decrease in the yield of monovinylhigh polymer production while retaining the ady ene. While poly t o t the lower vantages of high monovinylacetylene yield. temperatures is more efiicient with respect to The advantages of the new catalyst composiy d monovinyl ty n t s ne c ent in tion may be illustrated byacomparison with prior 5 th production p u o ime and p u t of art catalysts. Thus, applying the technique dea alyst is l wer. he pr uct n of p lymers scribed by Carter and Downing (United States and the y ld f monovinyla etyl n va y with PatentNo. 2,048,838) using a catalyst composed catalyst composition but all prior art catalysts of 1340 gms. cuprous chloride, 515 gms. ammoshow the temperature effect described. The nium chloride, 40 gms. 37% hydrochloric acid 40 priorart processes have been necessarily carried and 575 gms. of water, operated in a 4500 cc. out under conditions which represented a com- 4 catalyst tube, horizontally agitated at 180 R. P. p o se b twee h se; favoring h polymer M., and possessing a tube length of 37.2 cm. and

Production, and those favoring h y eld o diameter of 12.4 cm., acetylene was, introduced 5 monovinylacetylene. at a speed to permit a 23 second contact time in It is an object\ of this invention to carry out the catalyst chamber. The efiectof temperature the polymerization of acetylene to nonbenzenoid is shown by the data of Table I. polymers thereof under more eificient operating conditions than have heretofore been known or Table I used. It is a further object of the invention to 5o polymerize acetylene in the presence of a catalyst a. composition which gives maximum operating ef- Temperature, C. sion (EH2 ratio* ficiency, having due regard for both polymer MVA D production and monovinylacetylene yield. vA still further object is to provide a catalyst composition 'which gives good monovinylacetylene yield under conditions promoting high polymer production. Further objects will appear hereinafter.

. Percent 7.

HM Quote It will be observed that this catalyst contains a ratio of ammonium to cuprous chloride approximating 3CU2CI2.4NH4C1 and that this composition is not completely dissolved at the 50 C. operating temperature. With this catalyst, the results are typical of the prior art catalysts; e. g., with increased temperature, increased conversion and decreased MVA/DVA ratio. It has now been found, however, that a catalyst, approaching a composition Cu2Cl22NH4Cl may have a slightly lower conversion eillciency at any chosen temperature. but the MVA/DVA ratio will be superior, showing a 'much reduced temperature coefficient. The results with such a catalyst are shown in Table II. In this case, operation was carried out exactly as before, but the catalyst was composed of 1110 gms. CuzClz, 545 grns. NI'LlCl, 830 gms. H and 42 gms. 37% HCl.

DVA, as in Table I, includes all products other than monovinyl acetylene.

As will be seen from a comparison of the data of Table I with Table II for the same temperature and conversion, the MVA/DVA ratio is substantially better and only slightly affected by temperature in the case of the new catalyst. This discovery of a catalyst wherein there is practically no variation in the MVA/DVA ratio with change of temperature is unexpected. This catalyst has the advantage that the temperature range favoring the greatest gross production may be used without disturbing the MVA/DVA ratio.

With regard to the operation and general composition of the catalyst of this invention, one

essential improvement in operating technique is that it will be possible to carry the reaction tem perature above 50 C. and obtain equal or superior yields to those previously obtained at 50 C. It is preferred that this catalyst be used in a continuous process such as that of Carter and Downing (loc. cit.). In this process, the acetylene stream contacts the agitated catalyst, the gases leaving the reaction chamber are partially condensed and fractionated, theproducts of reaction are removed, and the unreacted acetylene is recirculated to the reaction chamber. Any gas velocity may be used which is sufficient to carry off the products of the reaction. I is preferred that the gas velocity .be high enough to remove the products before a substantial amount of divinylacetylene is formed. While the continuous process of Carter and Downing is recommended, the new catalyst is likewise effective in other processes for producing nonbenzenoid polymers of acetylene and in batch as well as continuous Cuprous chloride frequently contains cuprous oxide, cupric oxide and cupric chloride as impurities. The addition of a small amount of hydrochloric acidwill convert the oxides to the respective chlorides. The cupric chloride is reduced to cuprous chloride by means of metallic copper. Higher acidity within narrow limits will not prevent satisfactory operation, but if more than 0.6% hydrogen chloride is added over the quantity necessary to convert all of the copper salts to cuprous chloride, the efficiency will decrease and if more than 5% is added, objectionable by-products are formed. The acid necessary for optimum production varies with the quality of the cuprous chloride. Best results are obtained if hydrogen chloride is added to the catalyst before charging with acetylene, until the point is reached where the pH suddenly drops from about 4 or 5 to a pH of less than 1 as measured with the glass electrode.

The sole purpose of added copper metal is to maintain the copper chloride in the cuprous state. If cupric salts are absent and the gases are kept free of oxidizing agents such as air, the presence or absence of metalliccopper cannot be detected from the nature of the products obtained. As a safety measure, realizing the ease of oxidation of cuprous salts, the addition of copper powder in a quantity equal toabout 4% of the weight of the catalyst is desirable. However, if preferred, the same end is accomplished by having copper present as one element of the reaction system which is in contact with the catalyst, as, for example, copper paddles in the agitator blades of the reactor which may be replaced as consumed.

The composition of this catalyst with respect to cuprous chloride and ammonium chloride should approach that dictated by the formula Obviously, slight deviations from this ratio will not result in serious changes in efficiency, but

essentially, it is preferred that the molar ratio of NH4C] to C'J. 2C12 should be between 1.7 and 2.2 or substantially 2, as indicated by the formula, which corresponds to a weight ratio of 0.54. The concentration of this salt mixture in water should slightly exceed saturation so as to produce a small amount of solid phase in the solution at-the operating temperature for best mechanical and chemical efliciency, though this is not essential. has been found that the phase diagram of and water show a composition which is saturated with respect to Cl12C12.2NH4C1 at about 33% water at C. The saturation point varies with tem-' perature. A saturated solution of this composi tion is a good catalyst and has the advantage of being entirely in the liquid phase before saturation with acetylene. It has been found, however, that the efllciency of the catalyst can be further improved by the use of a higher percentage of water. v'Ihus, aparticularly desirable catalyst possesses the composition cuprous chloride 37%, ammonium chloride 20% and water 43%. Contrary to the. effect obtained by dilution of most solutions of a single solute in water, the dilution of this solution having two solutes (NHlCl and CuzClz) does not decrease saturation but increases it, and a small amount of solid phase appears. While solutions having a solid phase are especially desirable, the solid phase must be kept.

sufficiently small so as not to interfere with the areas" circulation of the catalyst, i. e., the fluidity of the solution must be maintained. This requirement is further complicated by the fact that when the solution is charged with acetylene in the reaction chamber, the solubility of cuprous chloride is further decreased, thereby increasing the solid phase present.

- Catalyst compositions within the close approximate range of the preferred catalyst have been tested, and for the purpose of a specific disclosure,

the particularly eiiective range includes compositions containing a molecular ratio of NH4C1 to CuaCl: of 1.7- to 2.2, which corresponds to a weight ratio of 0.46 to 0.59%, dissolved or suspended in to 50% of water. As will be seen, these ranges include a narrow band of compositions containing solutions of cuprous and ammonium chlorides in' approximately the molecular proportion of one of the former to two of the latter.

20 The following catalyst is particularly preferred 7 '30 The inference is not to be drawn that the cuprous and ammonium salts must exist in solution as the compound Cll2C12.2NH4C1; it is merely stated that they should be present in solution in approximately the radio to form this compound. Though it is believed that the conditions'specified favor a maximum concentration of this compound and that this fact is responsible for the eiiiciency of the catalyst, this is of purely theoretical signiflcance and has no essential bearing on the 40 quantities used or the results obtained.

In the discussion and appended claims referring to cuprous chloride, it is assumed that the molecular formula of cuprous chloride is CuaClz with a molecular weight of 198.1 and the proportions of materials have been given on this basis.

A method has been described for the polymerization of acetylene to nonbenzenoid polymers thereof in such manner as to increase the yield of monovinylacetylene and also to obtain a high with a more eflicient catalyst than those of-the prior art. It is to be understood that suitable changes may be made in the details of the invention without departing from the spirit thereof and that such changes are intended to be included within the scope of the appended claims.

'We claim:

1. A process of producing vinylacetylene, which comprises catalyzing the polymerization of acetylene with ammonium chloride and cuprous chloride in the molecular proportion mole of ammonium chloride mole of cuprous chloride polymer production. This method is carried out equals between 2. A process of producing vinylacetylene, whic comprises catalyzing\ the polymerization of acetylene with ammonium chloride and cupro chloride in the molecular proportion mole of ammonium chloride mole of cuprous chloride mole of ammonium chloride molrof cuprous chloride equals between ii? 2.2 T -1" and about 0.6% by weight of hydrogen chloride.

,and water in the amount of 30 to by weight.

4. A process of producing vinylacetylene, which comprises polymerizing acetylene at a temperature of about to C. in the presenceof a catalyst which consists of 36 to 38% cuprous chloride, 19 to 21% ammonium chloride and 41 to 45% water, and removing the resultingvinylacetylene together with the unreacted acetylene from the catalyst before a substantial amount of divinylacetylene is formed. 1

5. A process of producing vinylacetylcnc, which comprises polymerizing acetylene at a temperature of about 65 to 75 C. in the presence of a catalyst which consists of 36 to 38% cuprous chloride, 19 to 21% ammonium chloride, 41 to 45% water, and about 0.6% hydrogen chloride, metallic copper being present in quantities sumcient to keep the copper chloride in the cuprous 'state, and removing the resulting vinylacetylene together with the unreacted acetylene from the catalyst before a substantial amount of divinylacetylene is formed.

6. Aprocess of producing nonbenzenoid polymole of ammonium chloride mole of cuprous chloride eduais between ALBERT 8. CARTER.

nowann w.-

and water in the amount of 3.0 to 50% by weight. 

